EP0070497B1 - Nichttoxische Stabilisatormischung für halogenhaltige Polymere - Google Patents
Nichttoxische Stabilisatormischung für halogenhaltige Polymere Download PDFInfo
- Publication number
- EP0070497B1 EP0070497B1 EP82106237A EP82106237A EP0070497B1 EP 0070497 B1 EP0070497 B1 EP 0070497B1 EP 82106237 A EP82106237 A EP 82106237A EP 82106237 A EP82106237 A EP 82106237A EP 0070497 B1 EP0070497 B1 EP 0070497B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stabilizer
- toxic
- halogen
- containing polymers
- pvc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003381 stabilizer Substances 0.000 title claims description 39
- 239000000203 mixture Substances 0.000 title claims description 26
- 231100000252 nontoxic Toxicity 0.000 title claims description 5
- 230000003000 nontoxic effect Effects 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 title claims description 5
- 229910052736 halogen Inorganic materials 0.000 title claims description 4
- 150000002367 halogens Chemical class 0.000 title claims description 4
- -1 didodecyltin-bis-thioglycolic acid ester Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 11
- 239000004800 polyvinyl chloride Substances 0.000 description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- 241000700159 Rattus Species 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000000087 stabilizing effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- CMCOFAYLDYIEBR-UHFFFAOYSA-L 2-[carboxymethylsulfanyl(dioctyl)stannyl]sulfanylacetic acid Chemical class [O-]C(=O)CS.[O-]C(=O)CS.CCCCCCCC[Sn+2]CCCCCCCC CMCOFAYLDYIEBR-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- VDEKURXOWJYWCG-UHFFFAOYSA-N dodecyltin Chemical compound CCCCCCCCCCCC[Sn] VDEKURXOWJYWCG-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RPPZINJJZONDRV-UHFFFAOYSA-K 2-[bis(carboxymethylsulfanyl)-dodecylstannyl]sulfanylacetic acid Chemical class CCCCCCCCCCCC[Sn](SCC(O)=O)(SCC(O)=O)SCC(O)=O RPPZINJJZONDRV-UHFFFAOYSA-K 0.000 description 1
- IGMYAFRPSRRXNA-UHFFFAOYSA-L 2-[dibutyl(carboxymethylsulfanyl)stannyl]sulfanylacetic acid Chemical class [O-]C(=O)CS.[O-]C(=O)CS.CCCC[Sn+2]CCCC IGMYAFRPSRRXNA-UHFFFAOYSA-L 0.000 description 1
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 description 1
- XHMPRTGGXOYMCK-UHFFFAOYSA-N 8-methyl-2-sulfanylnonanoic acid Chemical group CC(C)CCCCCC(S)C(O)=O XHMPRTGGXOYMCK-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 231100000037 inhalation toxicity test Toxicity 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 210000004324 lymphatic system Anatomy 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical group [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- QONBXEOLXRAITN-UHFFFAOYSA-K trichloro(dodecyl)stannane Chemical class CCCCCCCCCCCC[Sn](Cl)(Cl)Cl QONBXEOLXRAITN-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
Definitions
- organotin stabilizers for the light and heat stabilization of halogen-containing polymers, in particular polyvinyl chloride and PVC copolymers, has long been known.
- FR-A No. 2109945 proposes mixtures of dialkyl and monoalkyltin stabilizers with alkyl radicals having 1 to 18 carbon atoms for PVC stabilization, the monoorganotin compound being said to make up the lower proportion in the mixture.
- the optimum effect is determined between 20 and 50%.
- PVC resins are stabilized with a mixture of mono- and di-n-octyltin thioglycolates, at least 70% of the monocomponent should be present, with advantageous properties in certain cases.
- EP-A No. 32106 also describes a stabilizer mixture of mono- and dioctyltin thioglycolates with 50 to 75% mono fraction, C 10 to C 16 alkyl thioglycolates being provided as thioglycolate residues.
- Conventional stabilizers such as dibutyl or octyltin thioglycolates, in particular in a mixture with the corresponding mono compounds, have a particularly favorable synergistic effect with a mono content of about 25 to 30% by weight with regard to the stabilizer effect.
- the excellent heat-stabilizing effect of the stabilizer mixtures according to the invention is all the more astonishing since the tin content, for example of the stabilizer mixture with the isooctylthioglycolate residue with 13.4% tin content, is considerably below that of the comparative stabilizer which contains 17.5% tin.
- the stabilizing effect of the inventive Dodecylzinn stabilizer mixtures increases in spite of even lower tin content (11.5% and 9% when dodecyl or Tetradecylthioglykola t) from only insignificantly. So far, it has been the case for all known organotin stabilizers that the stabilizing effect essentially depends on the tin content of the product, ie the effect decreases significantly as the tin content decreases.
- the stabilizer mixture according to the invention has the further advantage that it has even lower toxicity values than the conventional organotin stabilizers and can therefore be classified as non-toxic.
- the migration of the stabilizer from the PVC is important; understandably, it should be as low as possible.
- the migration of the stabilizer mixture according to the invention is very much lower than with other organotin stabilizers. It is below 0.2 ⁇ g tin / dm 2 test foil (compared to 5 ⁇ g tin / dm 2 for dioctyltin thioglycolates). In both cases the amount of stabilizer in PVC was 1.5% by weight.
- the stabilizer mixture according to the invention is therefore particularly suitable in several respects for packaging materials based on PVC or copolymers, which are used for the packaging of foods and pharmaceuticals or in the medical field, for example for blood preserves, plastic tubes for infusions, where particularly low toxicity values are required.
- the stabilizer mixture according to the invention is non-toxic and, owing to the extremely low migration compared to other organo, can Tin stabilizers get into the packaged goods in considerably smaller quantities.
- the amount of stabilizer used can be kept low from the outset due to the good stabilizing effect.
- the stabilizer mixture according to the invention is also low in odor and has a low volatility. In the thermal processing of many z. Organotin stabilizers currently in use can cause considerable annoyance to personnel due to the released stabilizer. The stabilizer mixture according to the invention does not have these disadvantages due to its high boiling points and low vapor pressure.
- the dodecyltin stabilizer components can be prepared by known processes from the corresponding dodecyltin chlorides or oxides and thioglycolic acid esters.
- the stabilizer mixture according to the invention is optionally used together with other known stabilizers, stabilizing auxiliaries, antioxidants, UV stabilizers, lubricants, plasticizers, etc. They are used in amounts of 0.1 to 3, in particular 1 to 2,% by weight, based on polymers. Stabilizer effect
- test temperature was 185 ° C. 2% Naftolube "Fol was added as a lubricant.
- a previously customary stabilizer was used as the comparative stabilizer, namely di-n-butyltin bisthioglycolic acid isooctyl ester with 25% content of mono-n-butyltin tristhioglycolic acid isooctyl ester.
- the tin content of this stabilizer is 17.5%.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US28419681A | 1981-07-17 | 1981-07-17 | |
US284196 | 1981-07-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0070497A1 EP0070497A1 (de) | 1983-01-26 |
EP0070497B1 true EP0070497B1 (de) | 1984-10-03 |
Family
ID=23089251
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82106237A Expired EP0070497B1 (de) | 1981-07-17 | 1982-07-13 | Nichttoxische Stabilisatormischung für halogenhaltige Polymere |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0070497B1 (nl) |
JP (1) | JPS5859248A (nl) |
BE (1) | BE893860A (nl) |
DE (2) | DE3223733A1 (nl) |
FR (1) | FR2509741A1 (nl) |
GB (1) | GB2102433B (nl) |
IT (1) | IT1156101B (nl) |
NL (1) | NL8202252A (nl) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2599373B1 (fr) * | 1986-05-30 | 1989-06-16 | Ciba Geigy Ag | Compositions a base de poly-(chlorure de vinyle) stabilisees par des composes laurylstanniques, application de ces compositions et procede pour stabiliser des matieres a mouler |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1346999A (en) * | 1970-10-02 | 1974-02-13 | Interstab Ltd | Stabilisers for vinyl chloride resins |
GB1510974A (en) * | 1975-05-19 | 1978-05-17 | M & T Chemicals Inc | Stabilized vinyl chloride resins |
EP0032106B1 (de) * | 1979-12-07 | 1983-06-01 | Ciba-Geigy Ag | Gemische von n-Octylzinn-Verbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung als Stabilisatoren für halogenhaltige Thermoplaste |
-
1982
- 1982-06-03 NL NL8202252A patent/NL8202252A/nl not_active Application Discontinuation
- 1982-06-25 DE DE19823223733 patent/DE3223733A1/de not_active Withdrawn
- 1982-06-28 IT IT22080/82A patent/IT1156101B/it active
- 1982-07-13 DE DE8282106237T patent/DE3260900D1/de not_active Expired
- 1982-07-13 EP EP82106237A patent/EP0070497B1/de not_active Expired
- 1982-07-14 JP JP57121374A patent/JPS5859248A/ja active Granted
- 1982-07-15 FR FR8212344A patent/FR2509741A1/fr active Granted
- 1982-07-16 GB GB08220659A patent/GB2102433B/en not_active Expired
- 1982-07-16 BE BE0/208610A patent/BE893860A/fr not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
EP0070497A1 (de) | 1983-01-26 |
GB2102433A (en) | 1983-02-02 |
BE893860A (fr) | 1983-01-17 |
NL8202252A (nl) | 1983-02-16 |
DE3260900D1 (en) | 1984-11-08 |
JPH0160178B2 (nl) | 1989-12-21 |
DE3223733A1 (de) | 1983-05-26 |
GB2102433B (en) | 1985-01-30 |
FR2509741B1 (nl) | 1985-01-18 |
JPS5859248A (ja) | 1983-04-08 |
IT1156101B (it) | 1987-01-28 |
FR2509741A1 (fr) | 1983-01-21 |
IT8222080A0 (it) | 1982-06-28 |
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